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  The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ - Ionothermal Synthesis, Crystal Structures, and Chemical Bonding

Groh, M. F., Müller, U., Isaeva, A., & Ruck, M. (2019). The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ - Ionothermal Synthesis, Crystal Structures, and Chemical Bonding. Zeitschrift für anorganische und allgemeine Chemie, 645(3), 161-169. doi:10.1002/zaac.201800441.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0003-31D8-2 Version Permalink: http://hdl.handle.net/21.11116/0000-0003-31DE-C
Genre: Journal Article

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 Creators:
Groh, Matthias F.1, Author
Müller, Ulrike1, Author
Isaeva, Anna1, Author
Ruck, Michael2, Author              
Affiliations:
1External Organizations, ou_persistent22              
2Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863444              

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 Abstract: The intermetalloid clusters [M2Bi12](4+) (M = Ni, Rh) were synthesized as halogenido-aluminates in Lewis-acidic ionic liquids. The reaction of bismuth and NiCl2 in [BMIm]Cl5AlCl(3) (BMIm = 1-butyl-3-methylimidazolium) at 180 degrees C yielded black, triclinic crystals of [Ni2Bi12][AlCl4](3)[Al2Cl7]. Black, monoclinic (P2(1)/m) crystals of [Rh2Bi12][AlBr4](4) precipitated after dissolving the cluster salt Bi12-xRhX13-x (X = Cl, Br; 0 < x < 1) in [BMIm]Br4.1AlBr(3) at 140 degrees C. In the cationic cluster [Ni2Bi12](4+), the nickel atoms center two base-sharing square antiprisms of bismuth atoms (symmetry close to D-4h). The valence-electron-poorer rhodium-containing cluster is a distorted variant of this motif: the terminating Bi-4 rings are folded to bicyclic butterflies and the central square splits into two dumbbells (symmetry close to D-2h). DFT-based calculations and real-space bonding analyses place the intermetalloid units between a triple-decker complex and a conjoined Wade-Mingos cluster.

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Language(s): eng - English
 Dates: 2019-01-132019-01-13
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Method: -
 Identifiers: ISI: 000459876900007
DOI: 10.1002/zaac.201800441
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Title: Zeitschrift für anorganische und allgemeine Chemie
  Other : J. Inorg. Gen Chem.
  Other : Journal of Inorganic and General Chemistry
  Abbreviation : Z. Anorg. Allg. Chem.
Source Genre: Journal
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Publ. Info: Leipzig, Weinheim : Verlag Johann Ambrosius Barth / Wiley-VCH
Pages: - Volume / Issue: 645 (3) Sequence Number: - Start / End Page: 161 - 169 Identifier: Other: 1521-3749
ISSN: 0044-2313
CoNE: https://pure.mpg.de/cone/journals/resource/954925453895